Insecticide



.cedures. v I

Specific problems which-are not met in satisfactory fashion by the use of phenothioxin com- Patented Sept. 28, 1 943 Curtis E. Dieter, George, E. Lynn, and Bernard J. Thiegs, Midland, Mich, assignors to The Dow Chemical Company, Mi

tion of Michigan gland, Mich, a corpora- No Drawing. Application May 16.19 42,

\ Serial N0. 443,284

5 Claims. (01. 167-30) I This invention relates to insecticides and is "phenothioxin compound as herein employed particularly concerned with compositions comprising di-(4-. chloro-phenoxy) -methane and 'a phenothioxin compound.

Extracts of. insecticidal plant products have sion of adequate supplies of such plant products, efforts are being made to 'employ phenothioxin and other synthetic organic toxicants as-substitutes therefor. Phenothioxin and its derivatives are relatively non-injurious to vegetation", but do not have suflicient toxicity against many com- 1 mon insect pests to warrant their. recommendafor use in general control pro tion as satisfactory either or both of these organisms requires immediate and effective treatment if substantial injury is to be avoided; The problem is'further complicated by the tender nature of the'vegeta tive growth affected, whereby many toxicant materials ordinarily suitable for general control cannot be used without materially injuring the'plant.

. Among the objects of the present invention is to provide toxicant mixtures comprising 'pheno thioxi'n and phenothioxin compounds which mix been widely used for the control of insect pests. Because of the difiiculties attending the provitures will be more quickly and-more permanently toxic to common agricultural and household pests than many compositions at present"em ployed. A further object is'to provide a toxicant product comprising a. mixture of cheap and readily synthesizable compounds which will not be' characterized by. those properties of irritation and toxicity to humans with which many other activating toxic'an'ts' displaying a synergistic actlon as regards insect and mite toxicity. Other objects of the invention will become apparent from the following description and examples.

According to the present invention di-(4-chlo- 40 synthetic toxicants are identified. -A still vfurther object is to supply a mixture of mutually ro-phenoxy) -methane is mixedwith one or a plu- I rality of phenothioxin compounds to obtain toxicant mixtures. When compounded in standard type parasiticidlal' compositions. these toxicant 'mixturesexert-a toxicity against insects and mites those having thefonnula:

compound in combination with di-(4-chloro-phenoxy)-methane and the usual diluents and carriers without injury to'plant growth. A preferred group of toxioants fallingwithin the scope of the; expression phenothioxin compounds are (5) j whereinR is. selected from .the group consisting of hydrogen, ml of the benzene series, cyclo- I} alkyl, alkyl containing at least 6 carbon atoms, and halogen, and n represents 0, 1-, 'or- 2. Mixtures of the foregoing compounds with di-(4-l chloro'- phenoxy)-methanehave been found to exert ,a synergisticeffec't as. regardscontr'ol of common agricultural and household-pests and particularly red spider and Mexican bean beetle.

In carrying out the invention, the dl-(4-chlorophenoxy) -methane and phenothioxin compound may be mixed together in any suitable'-manner, 4 e. g. bygrinding, simple mixing, dissolving, one I in the other, etc. materials employed vary with the particular phenothioxin compound concerned, the parasite to The exact proportions of able concentration of the resulting' mixture may be applied for pest control, with from about 0.001 I to 3 per cent by weight in spray compositions.

andfrom about -1 to 5 per cent in dust mixtures having. been found satisfactory in most instances.

The'toxicant mixturesmay be compounded 'with various 'inert carriers such as diatomaceous earth, bentonite, talc," sulfur, wood-flours, inorganic phosphates, or lime'to form agricultural dusts adapted to be applied in standard dusting equipment. IfdesirerL-such dusts may be employed as concentrates and subsequently.

dispersed in water or other liquid c'aniersto form sprays. Theitoidcanrt mixtures mayalso be in- D Any suitterials as inorganic pigments, organic dyes, acid lead arsenat, lime sulfur, pyrethrum, rotenone, organic thiocyanates, sulfur, copper sprays, and the like.

The several examples are illustrative with respect to the particular compounds, compound mixtures, and concentrations employed, but are not to be construed as limiting the invention.

Examrns 1 parts by weight of di-(4-ohloro-phenoxy)- methane, 10 parts of phenothioxin, and 80 parts of diatomaceous earth were ground together in a ball mill to form a concentrate containing 20 per cent by weight of toxicant mixture. 0.25 pound of sodium lauryl sulfate and 2.5 pounds of the concentrate were dispersed in 100 gallons of water to'obtain a spray mixture comprising 0.5 pound of the mixed toxicant. This spray composition was applied to bean foliage for the control of red spider and found to give a kill of 83.4 per cent without causing injury to the leaves of the host plant. In control'determinations an aqueous dispersion of 0.25 pound of di-(4-chlorophenoxy) -methane per 100 gallons gave a kill against red spider of 30.5 per cent, and one comprising 0.25 pound of phenothioxin per 100 gallons gave akill of 37 per cent.

EXAMPLE 2 In a similar manner di-(4-chloro-phenoxy)- methane was compounded with monochlorophenothioxin and the resulting concentrate dispersed in water to form a spray which was applied for the control of red spiders; A spray composition comprising 0.5 pound of the mixed toxicant per 100 gallons gave an average kill of 98 per cent. A composition comprising 0.25 pound of monochloro-phenothioxin per 100 gallons gave a kill against red spider of 49 per cent.

EXAMPLE 3 In a series of determinations di-(4-chloro-.

phenoxy) methane was tested against the larva of Mexican bean beetle, both alone and in combination with a number of phenothioxin compounds. The phenothioxin compounds alone were also tested to determine their effectiveness as toxicants. The procedure followed comprised dissolving'the toxicant or toxicant mixture in an organic solvent such as benzene, acetone, or ether, wetting 80 parts by weight of diatoms.- ceous earth with sufilcient of the solution to contain 20 parts of toxicant, and thereafter mixing and Warming the diatomaceous earth to drive off the solvent. The resulting dust concentrate was then dispersed in water containing 0.25 pound of sodium lauryl sulfate per 100 gallons as a wetting and dispersing agent. The resulting spray compositions were then applied to been foliage infested with the test organism. Representative of the results obtained are the data set forth in the following table.

Table Pounds 5144-01110- ggggfig Pcr pheuoxy)- Supplementary toxicent 3 cent methane per control 100 gallons 3 No None 40 P henothioxin 0. 5 0 Pbenothioxin. 0.6 100 M onochloro-phenothioxim- 0. 5 0 m1 'hl firo-phenothioxin. 0. 6 100 Nnnn llll "t I ux Amend e (L 5 n .5.- mm ---l0-dioxide. 0.5 05 N uuu I "X -10-0Xid6 O. 5 0 Mi m "JO-oxide 0.5 05 Mono-dodecyl-phenothioxln 0. 5 3 Mono-dodecyl-phenothioxin 0. 5 9n lhenyl-pheuothioxin-lo- 0.5 0

oxide. 0.5 1- hengl-phenothioxin-lo- 0. 5 50 or e. None il-oaloro-phenothioxin-lO- 0.5 0

doxide. 0.5 il-cnloro-phenothioxin-lo- 0.5 00

dioxide. None Motgii-cyolohexyl-pheno- 0. 5 0

o u. 1 0.5 Mono-oyolohexyl-pheno- 0.5 60

thioxln. l-phenyl-phenothioxin. 0. 5 0 0.5.. 1-pheny1-phenothioxin 0.5 05

EXAMPLE 4 Other mixtures which may be similarly employed for the control'of-insect and mite pests include the following: I

The compositions as set forth above may be employed as dusts or sprays for the control of such representative insect and mite pests as red spider, Mexican bean beetle, thrips, scale organisms, aphis, tent caterpillar, etc. Mixture B is specifically designed for the control of household insects such as flies, mosquitoes, roaches, and the like.

Other phenothioxin compounds which may be employed in combination with di-(-chlorophenoxy) -methane include mono-(i-methyl- .phenyl) -phenothioxin, mono-2xenyl-phenothioxin, 3-n-hexyl-phenothioxin, Z-bIOmO-DhEDO- thioxin, 1.3-dichl0ro-phenothioxin, 3-tertiarybutyl-phenothioxin, 3-nitrophenothioxin, 3-benzyl-phenothioxin, mixed polyethyl-phenothioxin,

l-cyclohexyl-phenothioxin-IO-oxide, 3-cyclohex yl-phenothioxin-lO-dioxide, 3-tertiaryoctyl-phenothioxin-lO-oflde, mixed 'polyethyl-phenothioxin-lO-dioidde, etc.

We claim: F 1. An insecticidal composition comprising di- (4-ch1oro-phenoxy) -methane and-a phenothioxin compound as active toxice'nts'.

p 2. An insecticidal composition comprising as active toxicants di-(-chloro-phenoxy) -methane and a. phenothioxin compound having the 01' hydrogen, aryl of the benzene series, cyclo alkyl, alkyl containing'at least 6 carbon atoms,

. and halogen; and n represents one of the values 0, 1, and 2.

3.'An insecticidal composition comprising di- (4-chloro-phenoxy)-methane and phenothioxin as active toxicants.

4. An insecticidal composition comprising di- (4-chloro-phenoxy)-methane and mono-chlorophenothioxin as active toxicants.

5. An insecticidal composition comprising 'as an active toxicant a mixture of 10 parts by weight of di-(-chlorophenoxy).-methane with from 1 to 100 parts by weight of a phenothioxin compound.

CURTIS E. I" '7 GEORGE E. LYNN.

BERNARD J. THIEGS.

wherein R is selected from the group consisting 

